Study of the Mechanism of Degradation of Ladder-Like Polyhedral Oligomeric Silsesquioxanes by Fourier Transform Infrared Spectroscopy

Abstract

Polyhedral Oligomeric Silsesquioxanes (POSS) are one of the smallest silica nano particles. The presence of ordered ladder-like or cage conformation in their structure leads to remarkable thermal stability far greater than that for a linear polysiloxane. Reinforcement with nano particles is one of the recently favored strategy used to enhance the performance of polymers materials. The cyclic silica structure present in POSS ensures excellent thermal and mechanical stability. As a reinforcing filler, POSS can enhance the resistance of polymer matrix against pyrolysis and corrosion. In this paper, amine-terminated POSS with ladder like structure was synthesized by condensation of hydrolyzed aminosilane coupling agent. The ladder-like structure of POSS severely limits the motion of the chain backbone. The absence of phase transition for the synthesized POSS was confirmed by differential scanning calorimetry (DSC). Thermogravimetric analysis (TGA) was utilized to evaluate the thermal stability of POSS. TGA data show that the ladder-like POSS reported here has high char yield of about 75 % in nitrogen atmosphere and 54% in air atmosphere at 800℃. The TGA derivative curves show that the degradation of ladder-like POSS involves multiple stages and that the degradation rate is directly proportional to the heating rate. With the aid of Fourier Transform Infrared Spectroscopy (FT-IR), the cyclic structure of Si-O-Si bonding was determined to be the predominant structure. By analyzing the FTIR spectra of the cured POSS residue obtained at the specified temperatures, the detailed degradation mechanism of POSS was inferred. From the FTIR spectra of the low temperature cured samples, it was shown that the terminal silanol group was eliminated below 400℃. Some intermediate polymeric siloxane structures were observed by means of FT-IR and they eventually transitioned into silica which is the final product of pyrolysis of POSS.
 The presence of the FTIR transmission peaks at 1000 and 1100 cm-1, due to asymmetrical vertical and horizontal stretching of Si-O-Si, were the key evidence for the inferred ladder-like structure of POSS.